ES2468555T3 - Methods for manufacturing chlorinated hydrocarbons - Google Patents

Abstract

A process for the manufacture of 1,1,2,3-pentachloropropane, the process comprising: preparing 1,1,1,2,3-pentachloropropane by heating a reaction mixture comprising 1,1,1,3-tetrachloropropane , ferric chloride and chlorine to produce 1,1,1,2,3-pentachloropropane, wherein the reaction mixture optionally further comprises carbon tetrachloride in an amount of up to 50% by weight of the reaction mixture; and dehydrochlorinate 1,1,1,2,3-pentachloropropane in a dehydrochlorination reaction zone in the presence of ferric chloride to produce 1,1,2,3-tetachloropropene and hydrogen chloride, where 1,1,2 , 3-tetrachloroprene and hydrogen chloride are removed from the hydrochlorination reaction zone through distillation during the course of the dehydrochlorination reaction.

Description

Methods for manufacturing chlorinated hydrocarbons.

Technical field

This invention relates to methods of manufacturing chloropropenes from chloropropanes, and more particularly to the manufacture of 1,1,2,3-tetrachloropropene from 1,1,1,2,3-pentachloropropane.

Background

Chlorinated hydrocarbons are useful as raw materials for the manufacture of refrigerants, polyurethane blowing agents, biocides, and polymers. 1,1,2,3-tetrachloropropene, for example, is a commercially available product used as a raw material for the herbicide Trialate (S- (2,3,3-trichloro-2-propenyl) bis (1-methyl ethyl) carbamothioate). 1,1,1,2,3-pentachloropropane can be used as an intermediate for the manufacture of 1,1,2,3-tetrachloropropene. Methods for the manufacture of 1,1,2,3-tetrachloropropene are described in the art, including in US Pat. No. 4,535,194 and in the US Patent Document. of Number 4,650,914.

The US Patent Document No. US-A 2,478,008 describes a process for the preparation of 1,1,1,2,3-pentachloropropane starting from 1,1,1,2-tetrachloropropane using ferric chloride and chlorine (see Example 1, in column 3, line 4).

HW Davis et al., In "Preparation of 1,1,1,3,3,3-haxachloropropane", THIS JOURNAL, 73, 1382 (1951) describes a process for the preparation of 1,1,1,2,3 -pentachloropropane starting from 1,1,1,3-tetrachloropropane using chlorine gas in the presence of UV light (see the experimental section of this reference).

The US Patent Document No. 4,000,312 describes a process for the preparation of 1,1,2,3-tetrachloropropene starting from 1,1,1,2,3-pentachloropropane using KOH as a dehydrohalogenation agent (see Example 52 of this reference ). 1,1,1,2,3-pentachloropropane has been prepared through the chlorination of CH3CH2CCl3 in the presence of sunlight according to US Pat. of US-A-4,000,312.

GM Shakhnazaryan at., In "Synthesis and reactions of 4-substituted tetrahydro-5-oxo-2-furoic acids", Journal of Organic Chemistry of the USSR, MA 1 K NAUKA-INTERPERIODICA, RU, Vol. 4, January 1968 , pages 1527-1532, describes the dehydrochlorination of tetrachloropropane to give 1,1,3-trichloropropene in the presence of FeCl2 and ZnCl2 (see

page 1528 “Experimental” of this reference).

Summary

The present application describes new methods of manufacturing chlorinated hydrocarbons such as 1,1,2,3-tetrachloropropene from 1,1,1,2,3-pentachloropropane. These chlorinated hydrocarbons can be used, for example, as raw materials to produce fluorocarbons. 1,1,1,2,3-pentachloropropane is used as an intermediate to produce 1,1,2,3-tetrachloropropene. The methods can provide improved efficiency and provide synergy in combinations of chemical reactions.

In one embodiment, the systems and methods described herein include the manufacture of 1,1,1,2,3pentachloropropene, which includes dehydrochlorination of 1,1,1,2,3-pentachloropropane in a reaction zone. in the presence of ferric chloride to produce 1,1,2,3-tetrachloropropene and hydrogen chloride, wherein 1,1,2,3pentachloropropene and hydrogen chloride are substantially continuously removed from the reaction zone at as they form, through distillation.

In another embodiment, the systems and methods described herein include a process for the manufacture of 1,1,2,3-tetrachloropropene, which includes (i) reacting 1,1,1,3-tetrachloropropane with chlorine in the presence of ferric chloride to produce unrefined 1,1,1,2,3-pentachloropropane; (ii) feed unrefined 1,1,1,2,3-pentachloropropane into a reaction zone to transform unrefined 1,1,1,2,3-pentachloropropane into 1,1,2,3-tetrachloropropene and chloride hydrogen by dehydrochlorination, wherein 1,1,2,3-tetrachloropropene and hydrogen chloride are removed from the reaction zone during the course of the dehydrochlorination reaction, preferably feeding and substantially extraction of continuous way; and (iii) collect 1,1,2,3-tetrachloropropene.

In another embodiment, the systems and methods described herein include the manufacture of 1,1,2,3-tetrachloropropene, which includes (i) reacting carbon tetrachloride with ethylene in the presence of iron chlorides, iron metal, and a trialkyl phosphate in a first reaction zone to produce a reactor effluent containing 1,1,1,3-tetrachloropropane; (ii) distilling said reactor effluent to produce a stream of the distillation head and a stream of distillation tails, the stream of the distillation head comprising a solution of unrefined 1,1,1,3-tetrachloropropane comprising tetrachloride of unreacted carbon and zero or more of low boiling pollutants, and comprising the stream of 1,1,1,3-tetrachloropropane distillation tails, iron metal, iron compounds, one or more components of phosphorus-containing catalyst, and high boiling by-products; (iii) reacting in a second reaction zone the stream of the distillation head with chlorine in the presence of ferric chloride to produce 1,1,1,2,3-unrefined liquid pentachloropropane; (iv) feed unrefined product from (iii) to the third reaction zone, which is part of a reactive distillation process, the reactive distillation process equipment comprising a reaction zone, a separation zone, and a zone of condensation, to transform the unrefined 1,1,1,2,3pentachloropropane into hydrogen chloride and 1,1,2,3-tetrachloropropene, where hydrogen chloride and 1,1,2,3-tetrachloropropene are continuously withdraw from the reaction zone, and (v) recover the product of purified 1,1,2,3-tetrachloropropene.

In another embodiment, the systems and methods described herein include the manufacture of 1,1,2,3-tetrachloropropene, which includes: (i) reacting carbon tetrachloride with ethylene in the presence of iron chlorides, iron metal, and trialkyl phosphate, to produce a reactor effluent comprising 1,1,1,3-tetrachloropropane; (ii) distilling said reactor effluent to produce a stream of the distillation head and a stream of the distillation tails, the stream of the distillation head comprising a first solution of unrefined 1,1,1,3-tetrachloropropane which it contains unreacted carbon tetrachloride and zero or more of low boiling pollutants, and comprising the stream of 1,1,1,3-tetrachloropropane distillation tails, iron compounds, one or more phosphorus-containing catalyst components , and by-products of high boiling point; (iii) distilling the first solution of unrefined 1,1,1,3-tetrachloropropane from ii) to produce a substantially pure carbon tetrachloride stream, comprising more than 90 percent by weight (% by weight) of tetrachloride carbon, and a second solution of unrefined 1,1,1,3-tetrachloropropane comprising no more than 10% by weight of carbon tetrachloride; (iv) recycle a portion of the substantially pure carbon tetrachloride stream from (iii) to the reactor (i); (v) reacting the second solution of unrefined 1,1,1,3-tetrachloropropane from iii) with chlorine in the presence of ferric chloride under conditions effective to produce a reactor effluent containing 1,1,1, 2,3-pentachloropropane and ferric chloride; (vi) continuously feed the reactor effluent from (v) to a reactive distillation process, the reactive distillation process equipment comprising a reaction zone, a separation zone, and a condensation zone, to transform the 1,1,1,2,3-unrefined pentachloropropane in hydrogen chloride and 1,1,2,3-tetrachloropropene, where hydrogen chloride and 1,1,2,3-tetrachloropropene are removed continuously from the reaction zone, and (vii) recovering the 1,1,2,3-tetrachloropropene product.

In the embodiments one or more of the following characteristics may be included:

1,1,1,3-tetrachloropropane, ferric chloride and chlorine can be heated in a liquid mixture with carbon tetrachloride;

carbon tetrachloride may be present in an amount of up to 50% by weight of the reaction mixture, preferably in an amount of 3 to 30% by weight of the reaction mixture;

ferric chloride may be present in a catalytic amount, such as in a range of from 10 to 1,000 ppm, for example 10 to 1,000 ppm � 30 to 1,000 ppm � 50 ppm to 1,000 ppm;

the reaction temperature may be 40 ° C to 120 ° C, and the reaction pressure may be in the range of 6.9 kPa - 2.1 MPa (1-300 psig);

the process can be a continuous process, and 1,1,1,3-tetrachloropropane and chlorine can be fed continuously to a reaction zone containing ferric chloride; The ferric chloride can be fed continuously to a reaction zone, it can be fed periodically to a reaction zone; 1,1,1,3-tetrachloropropane and chlorine can be introduced with a feed ratio of 0.9 to 1.1 mole of chlorine per mole of tetrachloropropane;

The ferric chloride can be fed into a reaction zone at least once for 0.5 to 3 rotations of the liquid (where one rotation is the time calculated as the ratio of the amount of liquid in the reactor to the liquid flow rate at the outlet of the reactor);

The reagents are added and the products can be extracted continuously, substantially continuously, or in batches periodically.

One or more of the following additional features may also be included in the embodiments:

at least, a part of the process can occur in the equipment comprising a reaction zone, a separation zone, and a condensation zone; the separation zone may include a distillation component;

The hydrogen chloride may have a co-product of the process and can be removed from the reaction zone through a separation zone and a condensation zone; the hydrogen chloride co-product leaving the reaction zone contains impurities, such as one or more of 1,1,3-trichloropropene or carbon tetrachloride; carbon tetrachloride and / or 1,1,3-trichloropropene are recycled to the reaction zone through the condensation zone; the separation zone comprises an empty tube or a tube containing a filling or other structure suitable for the promotion of vapor-liquid contact, and the condensation zone comprises a suitable container to cause some of the components of the chloride chloride stream hydrogen, such as 1,1,3-trichloropropene or carbon tetrachloride, condenses as a liquid; unrefined 1,1,1,2,3-pentachloropropane can be continuously removed from the reaction zone; 1,1,1,2,3-pentachloropropane can be dehydrochlorinated to produce 1,1,2,3-tetrachloropropene, and the unrefined 1,1,1,2,3-pentachloropropane reactor effluent can be directly dehydrochlorinated , without prior purification and without catalysts or reagents added; and the 1,1,2,3-tetrachloropropene product may be substantially free of 2,3,3,3-tetrachloropropene.

In some embodiments, the methods provide a lower number of processing steps than those described in the art. In some embodiments, the methods avoid the use of certain reagents described in the methods of the art. In some embodiments, the methods reduce the waste streams produced in relation to the methods of the art.

The details of one or more embodiments of the invention are set forth in the accompanying drawings and in the description below. Other features, objects and advantages of the invention will be apparent from the description and drawings, and from the claims.

Description of the drawings

Figure 1 shows a continuous process to produce 1,11,2,3-pentachloropropane from a raw material containing 1,1,1,3-tetrachloropropane.

Figure 2 shows a continuous process for the manufacture of 1,1,2,3-tetrachloropropene from a raw material containing 1,1,1,2,3-pentachloropropane.

Figure 3 shows a two-step continuous process to make 1,1,2,3-tetrachloropropene from raw materials containing 1,1,1,3-tetrachloropropane and chlorine.

Figure 4 shows a three-step continuous process to make 1,1,2,3-tetrachloropropene from ethylene, carbon tetrachloride, and chlorine raw materials.

Figure 5 is a graph depicting the rate of formation of 1,1,2,3-tetrachloropropene versus time, in relation to Examples 2-4.

Figure 6 shows the laboratory equipment used in a continuous example process to produce 1,1,1,2,3pentachloropropane.

The reference symbols in the various drawings indicate similar elements

Detailed Description

1. Processes for the production of 1,1,1,3-tetrachloropropane

In some embodiments, 1,1,1,3-tetrachloropropane is produced as described in one of US20040225166A1, US2003000648709 or US20040027520.

Document US20040225166A1 describes a process for the synthesis of 1,1,1,3-tetrachloropropane in which a fraction of the catalyst and cocatalyst are separated after the reaction and recycled where the reaction mixture is distilled off in a catalyst recovery unit resulting in the formation of a "distillation head fraction". This distillation head fraction contains 1,1,1,3-tetrachloropropane and unreacted carbon tetrachloride, and some other components such as unreacted ethylene, or by-products such as perchlorethylene, 1,2-dichloroethane, 1- chlorobutane, chloroform, or trichloropropene. The distillation head fraction such as that described in US20040225166A1 can be further processed in the methods and processes described in the present invention, for example, the conversion of 1,1,1,3-tetrachloropropane to 1, 1,1,2,3-pentachloropropane.

In some embodiments, the distillation head fraction from the catalyst recovery unit as described in US20040225166A1 can be separated to produce a stream containing an increased concentration of 1,1,1,3-tetrachloropropane and a stream which contains an increased concentration of carbon tetrachloride In this case, the recovered carbon tetrachloride and the relatively low boiling by-products contained therein can be partially recycled to a 1,1,1,3-tetrachloropropane reaction, by example, to a reaction described in US20040225166A1. A small amount of carbon tetrachloride can be purged from the system, for example, as a residue, or as a raw material for other processes. Purging of carbon tetrachloride can be carried out to control the concentration of low boiling materials in the 1,1,1,3-tetrachloropropane reactor.

In some embodiments, the 1,1,1,3-tetrachloropropane production process can produce a product containing up to 50% by weight of carbon tetrachloride, for example, from 3 to 30% by weight, together with small amounts ( for example, less than 5% by total weight) of materials such as perchlorethylene, 1,2-dichloroethane, 1-chlorobutane, chloroform, or trichloropropene. In general, the 1,1,1,3-tetrachloropropane product does not contain more than trace amounts (for example, less than 1,000 ppm each) of water or tributyl phosphate or trialkyl phosphate.

In some preferred embodiments, 1,1,1,3-tetrachloropropane is produced by the reaction of carbon tetrachloride with ethylene in the presence of a catalyst as indicated below. Carbon tetrachloride (CCl4) and ethylene are reacted in the presence of iron metal, iron chlorides, and a trialkyl phosphate, such as tributyl phosphate (TBP) to produce 1,1,1 , 3-tetrachloropropane in a continuous or batch process. The excess carbon tetrachloride is fed to the reaction mixture, so that the liquid product contains unreacted carbon tetrachloride. The liquid product is distilled, producing a distillation head mixture of carbon tetrachloride and 1,1,1,3-tetrachloropropane, and a mixture of the distillation tails containing catalyst components (iron and phosphorus-containing species ), 1,1,1,3-tetrachloropropane, and by-products of high boiling point.

In general, the term "batch process" refers to a way of carrying out a chemical process in which the process starts with the reagents that are reacted under appropriate reaction conditions for a suitable time and become a product. . The process is then terminated, and the reaction mixture containing the product is collected. The reaction mixture is typically further processed in order to isolate and / or purify the product from the unreacted starting materials. On the other hand, the term "continuous process" refers to a way of carrying out a chemical process in which, once the process has stabilized, the reagents are added to a vessel in which the reaction takes place and the products are removed simultaneously. Ideally, a continuous process can be operated to convert a substantially continuous stream of starting materials into a substantially continuous stream of products. "Substantially continuously" or "substantially continuously" when referring to the addition of reagents, or the extraction of products or other operations (such as heating, cooling, stirring, etc.) carried out as a part of Chemical processes means that the operation is carried out for a period of time during the course of the process, in contrast to the batch or periodic development of such operations. The terms are not intended, however, to exclude the possibility of a periodic interruption in the operation.

The mixture of the distillation tails is generally partially recycled to the 1,1,1,3-tetrachloropropane reactor, and partly purged (for example, in some cases, the purge can control the degradation of the catalyst and the concentration of materials high boiling point in the system). The term "high boiling point" as used herein refers to materials that are either not volatile, or have normal boiling points greater than that of a preferred product, such as 1.1, 1,3-tetrachloropropane. The normal boiling point of 1,1,1,3-tetrachloropropane is approximately 155 to 160 �C. The head distillation mixture of CCl4 and 1,1,1,3-tetrachloropropane can be sent without further purification to a subsequent reaction step. Alternatively, some or most, for example, 0-100%, of the carbon tetrachloride can be separated from 1,1,1,3-tetrachloropropane, and some or most of the carbon tetrachloride can be recycled to the reactor of 1, 1,1,3-tetrachloropropane, while 1,1,1,3-tetrachloropropane is sent to the next reaction stage. It is preferred that the mixture going to the next reaction stage contains from 3 to 30% by weight of carbon tetrachloride, so that any excess over this amount can be separated and recycled or purged.

2. Processes for the production of 1,1,1,2,3-pentachloropropane

1,1,1,2,3-pentachloropropane can be formed by a process where 1,1,1,3-tetrachloropropane is reacted with chlorine in the presence of ferric chloride catalyst to produce 1,1, 1,2,3-pentachloropropane and hydrogen chloride.

Without wishing to be bound by theory, it is believed that 1,1,1,3-tetrachloropropane dehydrochlorides, in the presence of ferric chloride, producing 1,1,3-trichloropropene as an intermediate in situ, to which is added chlorine in a reaction also catalyzed by ferric chloride, to produce 1,1,1,2,3-pentachloropropane as shown below. The present process, however, is generally carried out in a single chemical operation, without the isolation or purification of the 1,1,3-trichloropropene intermediate before the reaction forming 1,1,1,2,3- Pentachloropropane, although unreacted 1,1,3-trichloropropene can be collected and recycled in the process. Preferably, the unrefined product from the process contains a ratio of at least 1.5: 1 by weight of 1,1,1,2,3pentachloropropane to 1,1,3-trichloropropene, more preferably at least 2: 1, 3 : 1, 5: 1, 9: 1,10: 1,100: 1,1,000: 1, �

5,000: 1 or greater.

In addition, dehydrochlorination catalyzed by ferric chloride can result in the formation of 1,1,2,3-tetrachloropropene as a desirable by-product formed according to the following scheme:

The 1,1,1,3-tetrachloropropane raw material used as the starting material for this process can generally be obtained by any convenient method. In some embodiments, the 1,1,1,3-tetrachloropropane raw material may contain up to 50% by weight of carbon tetrachloride, and up to 5% by total weight of chlorinated hydrocarbons such as perchlorethylene, chloroform, 1,2-dichloroethane, chlorobutane , trichloropropene, etc. The 1,1,1,3-tetrachloropropane raw material used generally contains no more than 1,000 ppm of each of water, trialkyl phosphate, alcohols, or other materials that bind strongly with or deactivate Lewis acid catalysts such like ferric chloride. The total amount of said deactivating compounds is preferably less than 1,000 ppm by weight. The chlorine raw material is generally substantially pure and dry; it contains less than 0.5% by weight of water, and more preferably less than 0.05% by weight of water.

The ferric chloride catalyst is generally anhydrous, does not contain more than 3% by weight of water. The ferric chloride catalyst is generally handled as a solid.

The reaction is generally carried out by heating a reaction mixture containing 1,1,1,3-tetrachloropropane, ferric chloride and chlorine to produce 1,1,1,2,3-pentachloropropane. The reaction mixture may also contain carbon tetrachloride, for example in an amount of up to 50% by weight of the reaction mixture, for example, 3 to 30% by weight. Ferric chloride is preferably present in the mixture in a catalytic amount, preferably 25,000 ppm or less, for example 5,000 ppm, 2,000 ppm, or 1,000 ppm or less. Ferric chloride may be present in an amount in the range of from 10 to 25,000 ppm, from 20 to 5,000 20 to 10,000 ppm, from 30 to 2,000 ppm, from 30 to 1,000 ppm, or from 50 to 2,000 ppm, or from 50 to 1,000 ppm for example.

In some embodiments, at least a part of the process is performed on equipment that includes a reaction zone, a separation zone and a condensation zone.

Hydrogen chloride is a coproduct of the process. In some embodiments, the hydrogen chloride co-product is removed from the reaction zone through a separation zone and a condensation zone. When hydrogen chloride leaves the reaction zone it may contain impurities, for example 1,1,3-trichloropropene and / or carbon tetrachloride. In some embodiments of the process, the separation zone may comprise an empty tube or a tube containing filler or other structure suitable for the promotion of vapor-liquid contact, and the condensation zone may comprise a suitable container to make some of the Hydrogen chloride stream components, such as 1,1,3-trichloropropene or carbon tetrachloride, condense as a liquid. In some embodiments of the process, hydrogen chloride leaving the reaction zone contains 1,1,3-trichloropropene and / or carbon tetrachloride and 1,1,3-trichloropropene and / or carbon tetrachloride are recycled to the reaction zone through the condensation zone.

In some embodiments of the process, the reaction temperature for the reaction to form 1,1,1,2,3pentachloropropane is in a range of 40 ° C to 120 ° C.

In some embodiments of the process, the reaction pressure is in a range of 6.9 kPa at 2.1 MPa (1 to 300 psig).

1,1,1,2,3-pentachloropropane can be produced in a semi-discontinuous or continuous process.

For a semi-discontinuous process, the 1,1,3-tetrachloropropane liquid raw material is generally placed with solid ferric chloride in a vessel equipped with means for stirring and temperature control. The mixture is generally heated and stirred at a temperature between 40 ° C and 120 ° C, while chlorine gas is introduced below the surface of the liquid at a rate sufficiently low so that the reaction temperature remains controllable, and high enough to consume a substantial fraction of the 1,1,3-trichloropropene intermediate, as it forms.

In a semi-discontinuous operation, the different process conditions must be regulated in order to maintain the concentration of 1,1,3-tetrachloropropene in the liquid below 20% by weight at all times during the reaction. In a continuous operation, the different process conditions must be regulated to maintain the concentration of 1,1,3-tetrachloropropene at steady state in the liquid below 5% by weight.

The hydrogen chloride co-product of the process that forms 1,1,1,2,3-pentachloropropane is generally allowed to escape from the reactor, for example, through a pressure control valve. The pressure is optionally controlled from 0 to 2.1 MPa (0 to 300 psig), and more preferably from 13.8 kPa to 0.7 MPa (2 to 100 psig). In some embodiments, the stream containing hydrogen chloride is cooled to condense organic materials such as carbon tetrachloride or 1,1,3-trichloropropene, and return these materials to the reactor.

When the process is performed in semi-discontinuous mode, it is not required to exactly match the rate of the chlorine feed with the production rate of 1,1,3-trichloropropene, but in some preferred embodiments, the speeds are adjusted so that match substantially. The speed of the chlorine feed can be controlled directly. The production rate of 1,1,3-trichloropropene can be controlled indirectly, and may vary over time. The production rate of 1,1,3-trichloropropene may be influenced by the concentration of the ferric chloride catalyst and the temperature. If too much chlorine is fed in relation to the production rate of 1,1,3-trichloropropene, then unreacted chlorine can exit the reactor with hydrogen chloride co-product. If too little chlorine is fed in relation to the production rate of 1,1,3-trichloropropene, then a relatively high concentration of 1,1,3-trichloropropene can accumulate in the reactor. This material can be consumed by the continuous addition of chlorine. But high concentrations of 1,1,3-trichloropropene may be somewhat undesirable, since this condition may produce higher levels of undesirable high boiling by-products. In the semi-discontinuous mode, the chlorine feed rate should preferably be controlled to limit the concentration of 1,1,3-chloropropene in the reactor liquid to between 0.03 and 20% by weight at any time during the reaction, and more preferably between 0.03 and 10% by weight.

Depending on the temperature and activity of ferric chloride, and the rate of feeding of the chlorine, the semi-discontinuous process may require, for example, 0.5 to 24 hours for its completion. The completion is generally marked by the conversion of more than 90% of the 1,1,1,3-tetrachloropropane fed to the products, and by the conversion of more than 90% of the resulting 1,1,3-trichlororopropene to the products .

For a continuous process, the 1,1,1,3-tetrachloropropane liquid raw material and the chlorine gas are generally fed substantially continuously to a reactor equipped with means for stirring and temperature control. The hydrogen chloride co-product is removed continuously, optionally through a pressure control valve. In some embodiments, the stream containing hydrogen chloride is cooled so that condensed organic materials, such as 1,1,3-trichloropropene and carbon tetrachloride, can be returned to the reactor. The liquid product can be removed continuously, for example through conventional means such as a pump with level control, etc. In some preferred embodiments, the chlorine gas is bubbled into the liquid.

Ferric chloride can be added substantially continuously or periodically. If the ferric chloride is added periodically, then a fixed amount of at least once per 0.5 to three rotations of the reactor liquid can generally be added, where the rotation time is calculated as follows. The flow rate of the liquid effluent from the reactor is F [liters / h], and the amount of liquid in the reactor is V [liters]; what they provide the

rotation time as τ [h] = V / F. The temperature of the reactor liquid is generally maintained between 40 ° C and

120 �C. The reactor pressure is generally maintained between 0 and 2.1 MPa (0 psig and 300 psig). The rotation time is generally between 0.5 hours and 24 hours. The concentration of ferric chloride in the reactor liquid is generally in the range of 30 ppm to 1,000 ppm, for example 30 ppm and 1,000 ppm, by weight. The ratio of the chlorine / 1,1,1,3-tetrachloropropane feed is preferably 0.90 to 1.10 mol / mol, and more preferably between 1.01 and 1.05 mol / mol.

Without wishing to be bound by any theory, it is believed that careful control of the ratio of the chlorine / 1,1,1,3-tetrachloropropane feed is useful for at least two reasons. First, if too little chlorine is fed, then excessive amounts of compounds containing six carbon atoms can be formed. It may be that such compounds of six carbon atoms are formed by the reaction of two molecules of three carbon atoms, such as two 1,1,3-trichloropropene molecules. Second, if too much chlorine is fed, then excessive amounts of materials can be formed on chlorine. Both circumstances could result in the misuse of valuable materials and the production of unnecessary quantities of waste.

In some embodiments, the 1,1,1,3-tetrachloropropane raw material contains from 0.0% by weight to 50% by weight of carbon tetrachloride. It is preferable that the 1,1,1,3-tetrachloropropane raw material should contain 3 to 30% by weight of carbon tetrachloride.

The reactor can be operated in order to produce very low concentrations of 1,1,3-trichloropropene in the effluent, for example, less than 3% by weight, or in order to produce considerable amounts, for example, greater than 3 % in weigh. If the intended application for 1,1,3-trichloropropene is to make 1,1,1,2,3-pentachloropropane, then it is preferable to operate the reactor in order to produce very low concentrations of 1,1,3-trichloropropene in the liquid effluent from the reactor, and return almost all of the 1,1,3-trichloropropene contained in the hydrogen chloride vent stream to the reactor. If there are other desirable applications for 1,1,3-trichloropropene, then the reactor can be operated in order to produce 1,1,3-trichloropropene, recoverable from the reactor's vent current, and 1,1,1 , 2,3-pentachloropropane, contained in the liquid effluent stream of the reactor. It is preferable in all cases to maintain low concentrations of 1,1,3-trichloropropene in the liquid effluent of the reactor.

The desired product produced by the processes described above is an unrefined 1,1,1,2,3pentachloropropane liquid. In some embodiments, the product also contains ferric chloride catalyst, and small amounts of one or more of the unreacted 1,1,1,3-tetrachloropropane, intermediate 1,1,3trichloropropene, byproduct 1,1,2, 3- tetrachloropropene. In some embodiments, the unrefined product includes a small amount of unwanted by-products such as hexachloropropane. Optionally, 1,1,1,2,3-pentachloropropane liquid is further purified. The concentration of 1,1,1,2,3-pentachloropropane in the unrefined liquid is generally greater than 50% by weight. In some embodiments, the unrefined liquid contains up to 30% by weight of carbon tetrachloride. The concentration of 1,1,1,3-tetrachloropropane in the unrefined 1,1,1,2,3-pentachloropropane product is generally less than 5% by weight. In some embodiments of the process, unrefined 1,1,1,2,3-pentachloropropane is removed from the reaction zone. In some embodiments of the process, unrefined 1,1,1,2,3-pentachloropropane is periodically removed from the reaction zone. In some embodiments of the process, unrefined 1,1,1,2,3-pentachloropropane is removed from the reaction zone substantially continuously.

Figure 1 represents an example of the manufacturing process of 1,1,1,2,3-pentachloropropane (HCC240db). As shown in Figure 1, 1,1,1,3-tetrachloropropane, carbon tetrachloride, ferric chloride, and chlorine are fed to a reaction zone. The reaction is maintained at a temperature such that at least a part of the reaction and the products move in the separation and / or condensation zone. At least a part of the hydrogen chloride product is removed by the exit of the condensation zone. The 1,1,1,2,3pentachloropropane product is removed from the reaction zone in a liquid effluent.

3. Processes for the production of 1,1,2,3-tetrachloropropene

1,1,2,3-tetrachloropropene can be formed by a process in which 1,1,1,2,3-pentachloropropane is dehydrochlorinated in the presence of ferric chloride catalyst to produce the product of 1.1 , 2,3-tetrachloropropene and the hydrogen chloride co-product.

The 1,1,1,2,3-pentachloropropane used for the preparation of 1,1,2,3-tetrachloropropene can be prepared by one of the aforementioned processes for the preparation of 1,1,1,2,3- pentachloropropane. In some embodiments, the unrefined 1,1,1,2,3-pentachloropropane reactor effluent from a reactor where 1,1,1,2,3-pentachloropropane is formed, is directly dehydrochlorinated without prior purification and no catalysts or reagents added.

In some embodiments, the 1,1,2,3-tetrachloropropene product is substantially free of 2,3,3,3-tetrachloropropene. The above mentioned dehydrochlorination catalyzed by ferric chloride can prevent the use of sodium hydroxide or aqueous alkali for the dehydrochlorination of 1,1,1,2,3-pentachloropropane.

The purified 1,1,1,2,3-pentachloropropane or the 1,1,1,2,3-unrefined pentachloropropane containing the ferric chloride catalyst is generally fed into a reactive distillation system. Alternatively, or in addition, the ferric chloride can be added separately to the system. This would certainly be necessary if purified 1,1,1,2,3pentachloropropane is used as the raw material.

Ferric chloride can be added during the course of the reaction and said addition can be continuous or periodic. When ferric chloride is added, ferric chloride can be added to the process periodically. For example, ferric chloride can be fed to the reaction zone at least once for 0.5 to 3 rotations of the liquid, and where one rotation is the time calculated as the ratio of the amount of liquid in the reactor at the flow of liquid at the outlet of the reactor. Alternatively, ferric chloride can be added continuously. The amount of ferric chloride maintained in the reaction zone is preferably a catalytic amount, for example, 50,000 ppm.

or less. Ferric chloride may be present in an amount in the range of from 10 to 50,000 ppm, from 100 to 25,000 ppm, or from 1,000 to 20,000 ppm, for example. In some embodiments, during the course of the reaction an amount is maintained in the range of 30 to 20,000 ppm by weight, for example 1,000 to 20,000 ppm, of ferric chloride in the reaction zone.

A process for the preparation of 1,1,2,3-tetrachloropropene can use reactive distillation. In general, such a process includes dehydrochlorination of 1,1,1,2,3-pentachloropropane in a reaction zone in the presence of ferric chloride to produce 1,1,2,3-tetrachloropropene and chloride. of hydrogen, wherein 1,1,2,3-tetrachloropropene and hydrogen chloride are removed from the reaction zone by distillation during the course of the dehydrochlorination reaction, for example, by withdrawing as they are formed, so continuous or substantially continuous. Preferably, the unpurified liquid product from the 1,1,1,2,3pentachloropropane reactor, which already contains the ferric chloride catalyst, is fed continuously to a reactive distillation system. The system may be equipped with a reaction zone, a separation zone, and a condensation zone. The feed enters the reaction zone, which is generally below the separation zone. The liquid in the reaction zone is heated and stirred. Any means can be used to provide agitation and heat. For example, agitation can be provided by means of a closed circuit of pumped circulation, or by agitation. Heat can be provided through a jacket over the container, or by internal heat exchangers, or by external heat exchangers. Preferably, the reactor liquid does not contain more than 1,000 ppm of each of water, trialkyl phosphate, alcohols, or other materials that bind strongly with or deactivate Lewis acid catalysts such as ferric chloride. The total of such deactivating compounds is generally less than 1,000 ppm by weight. Optionally, means for adding more ferric chloride catalyst are included. Such addition may be continuous or periodic.

The reactive distillation system can be operated in a continuous process where the reagent addition and product extraction are carried out at the same time.

When the process is carried out as a continuous process, a reagent solution comprising 1,1,1,2,3pentachloropropane and ferric chloride can be introduced periodically or substantially continuously into the reaction zone. The reagent solution may be an unrefined, partially purified or purified product from the 1,1,1,2,3-pentachloropropane preparation processes described above. The reagent solution used for the synthesis of 1,1,2,3-tetrachloropropene may also contain one or more of carbon tetrachloride, 1,1,3-trichloropropene, 1,1,1,3-tetrachloropropane, or hexachloropropane. The reaction zone may be substantially free of sodium hydroxide or aqueous sodium hydroxide.

In the reactive distillation system, the products can be removed from the reaction zone of the liquid reaction mixture, in addition by distillation.

In some embodiments, the liquid reaction mixture, which comprises unreacted 1,1,1,2,3-pentachloropropane, ferric chloride, nonvolatile material, and high boiling by-products, is removed from the zone. of reaction. The liquid reaction mixture can be removed continuously or substantially continuously from the reaction zone. Alternatively, the liquid reaction mixture can be periodically removed. The 1,1,1,2,3pentachloropropane that has not reacted contained in the liquid reaction mixture removed from the reaction zone can be substantially separated from other components and recycled in the reaction zone.

Generally, two product streams come out of the reactive distillation system. The stream of the distillation tails continuously or periodically removes high boiling materials or boiling materials such as unreacted 1,1,1,2,3-pentachloropropane, hexachloropropane, pentachlorohexene, hexachlorohexane, and chloride f Rich. The distillation head stream continuously removes 1,1,2,3-tetrachloropropene, hydrogen chloride, and, in some embodiments, unreacted 1,1,1,2,3-pentachloropropane products, 1 , 1,1,3-tetrachloropropane, and 1,1,3-trichloropropene. The distillation head stream generally removes carbon tetrachloride, if it is present in the feed.

Reactive distillation is generally performed using a reactive distillation equipment that includes a reaction zone, a separation zone, and a condensation zone. The separation zone is generally positioned vertically above the reaction zone. In a simple embodiment, the separation could comprise a tube. In some embodiments, however, the separation zone may contain a surface, for example, a filler material or other structures, suitable for promoting efficient contact of vapor and liquid streams. Consequently, the separation zone promotes the separation of the more volatile and less volatile components of the reaction mixture.

The liquid in the reaction zone contains the ferric chloride catalyst, most of the unreacted pentachloropropane, and some of the reaction products. The dehydrochlorination reaction generally occurs in the reaction zone. The separation zone is generally operated at a distillation head pressure of 13.3 to 79.8 kPa (100 to 600 torr), to provide a temperature at the distillation tails in the reaction zone that varies from 120 � C to 180 �C. The 1,1,2,3-tetrachloropropene product continuously leaves the reaction zone through the separation zone, together with the hydrogen chloride. In some embodiments, the separation zone maintains most of the 1,1,1,2,3-pentachloropropane that has not reacted in the reaction zone, and allows most of the 1,1,2,3 product -tetrachloropropene escape from the reaction zone.

In the condensation zone, the vapor stream generally cools, causing condensation of the unreacted 1,1,1,3,3-tetrachloropropene, 1,1,1,2,3-pentachloropropene, and components such as the carbon tetrachloride, 1,1,1,3-tetrachloropropane, and 1,1,3-trichloropropane. The uncondensed hydrogen chloride can be further purified or sent to another place for extraction or use. In some embodiments, a part of the condensate can be returned to the separation zone as a reflux liquid, and a part can be removed as a product. For example, approximately 10% of the condensed 1,1,2,3-tetrachloropropene can be removed as a product. The product can optionally be sent to a product purification system for further purification.

In some embodiments, a product purification system produces purified 1,1,2,3-tetrachloropropene product suitable for its intended application, and separates other components of the distillation head stream from the reactive distillation column. For example, carbon tetrachloride, 1,1,3-trichloropropene, and / or 1,1,1,3-tetrachloropropane can be recovered in suitably pure form, and, or recycled to any of the chemical processes mentioned Previously they employ the particular compound, or also send it to another application.

By operating the reactive distillation system at a sub-atmospheric pressure, and therefore at a reduced temperature, the formation of tar and polymeric material can be reduced. Continuous or periodic purging of the reaction zone can be extracted to maintain the concentration of the ferric chloride in a range of 1,000 ppm to 20,000 ppm by weight. This purge can also remove tars containing catalytically inactive iron and polymeric materials, in addition to catalyst poisons, if any. The purge can therefore be operated to maintain catalytic activity and to remove high boiling contaminants and contaminants that do not boil from the system.

The unrefined 1,1,2,3-tetrachloropropene product is generally removed continuously from the distillation head of the separation zone. Continuous extraction can reduce the amount of 1,1,2,3 tetrachloropropene in contact with the ferric chloride catalyst in the reaction zone. Although not bound by theory, it is believed that this reduces the likelihood of olefin reducing catalytically active ferric chloride to inactive ferrous chloride, which can help preserve the life of the catalyst. The product of the unrefined 1,1,2,3-tetrachloropropene distillation head can be re-distilled in a conventional manner to remove unwanted high or low boiling compounds.

Figure 2 represents an example process for the production of 1,1,2,3-tetrachloropropene. 1,1,1,2,3pentachloropropane and ferric chloride are fed to a reaction zone. The reaction zone is maintained at a temperature and pressure such that at least a portion of the reaction products move in the separation and / or condensation zones. At least a part of the hydrogen chloride product is removed by the exit of the condensation zone. At least a portion of the unrefined 1,1,2,3-tetrachloropropene product is condensed in the condensation zone and subsequently removed from the process.

Figure 3 represents a synergistic process for the production of 1,1,2,3-tetrachloropropene. 1,1,1,3-tetrachloropropane, ferric chloride, and chlorine, and optionally carbon tetrachloride (not shown), are fed to a reaction zone shown at the top of Figure 3. The reaction is maintained at a temperature such that at least a portion of the reaction products move in the separation and / or condensation zones. At least a part of the hydrogen chloride product is removed by the exit of the condensation zone. The 1,1,1,2,3-pentachloropropane product is removed from the reaction zone in a liquid effluent and subsequently introduced into a second reaction zone shown at the bottom of Figure 3. The second reaction zone it is maintained at a temperature such that at least a part of the reaction products move in the separation and / or condensation zone. At least a part of the hydrogen chloride product is removed by the exit of the condensation zone. At least a portion of the unrefined 1,1,2,3-tetrachloropropene product is condensed in the condensation zone and subsequently removed from the process.

Figure 4 represents an exemplary synergistic process for the production of 1,1,2,3-tetrachloropropene. Ethylene, iron metal, carbon tetrachloride, and trialkyl phosphate are introduced into a first reaction zone, shown near the top of Figure 4. The liquid effluent from the reactor passes to a first separation zone. , which separates the effluent from the first reactor in a stream of the distillation head and in a stream of the distillation tails. The stream of the distillation tails, which contains catalyst components, is partially returned to the first reaction zone and part is purged. The distillation head stream, which contains unreacted 1,1,1,3-tetrachloropropane and carbon tetrachloride product, passes to a second reaction zone, shown near the center of Figure 4. Chlorine and The ferric chloride catalyst is also introduced into the second reaction zone, where 1,1,1,2,3-pentachloropropane and hydrogen chloride are produced. At least some of the hydrogen chloride product is removed as a gas through the separation zones of the distillation and condensation head. At least some of the 1,1,3-trichloropropene by-product and the carbon tetrachloride solvent, and other volatile organic materials, are condensed and returned to the reaction zone through the separation and condensation zones. The liquid effluent from the second reaction zone contains at least 1,1,1,2,3-pentachloropropane product and the ferric chloride catalyst. This material is transferred to the third reaction zone, shown near the bottom of Figure 4. In the third reaction zone, 1,1,1,2,3-pentachloropropane is catalytically dehydrochlorinated to produce 1, 1,2,3-tetrachloropropene and hydrogen chloride. At least some of the 1,1,2,3-tetrachloropropene and hydrogen chloride products pass through the separation zone in the condensation zone, where some 1,1,2,3-tetrachloropropene condenses , and therefore separated from the hydrogen chloride gas. This partly purified hydrogen chloride gas is removed from the condensation zone. The condensed 1,1,2,3-tetrachloropropene product is partly returned to the separation zone as a reflux liquid, and is partly removed as a liquid product of unrefined 1,1,2,3-tetrachloropropene. The latter can be further purified by any known means. A stream of liquid purge is extracted from the third reaction zone. This stream contains ferric chloride catalyst, 1,1,1,2,3-pentachloropropane that has not reacted, and high-boiling or non-volatile by-products.

Examples

Examples 1-4. Formation of 1,1,2,3-tetrachloropropene

The equipment used in Examples 1-4 was a vacuum pyrex laboratory distillation column with 20 trays and 25 mm internal diameter, equipped with a 1 liter distillation flask and with means for pressure operation lower than atmospheric A pump continuously fed the liquid material directly to the distillation flask. An oscillating drawer-type reflux head allowed the controlled removal of a distillation head product. An independent pump periodically removed the liquid from the distillation flask.

Table 1 shows the test conditions for Examples 1-4. Figure 1 shows the rate of formation by the distillation head of the 1,1,2,3-tetrachloropropene product.

Table 1 Conditions for Examples 1-4

Example number

one 2 3 4

Pressure in the distillation head

kPa (torr) 37.2 (280) 65.8 (495) 63.8 (480) 46.5 (350)

Temperature in the distillation tails

�C 159 - 160 173-177 169-179 154-157

Residence time of the distillation tails

H 4,5 7 8 8

Liquid power supply

Synthetic Synthetic Tetrachloropropane Chlorination Tetrachloropropane Chlorination

Composition of liquid feed

1,1,1,2,3- pentachloropropane

% in weigh 45.0 90.8 61.0 80.0

Miscellaneous Chlorocarbons

% in weigh 55.0 9.2 39.0 20.0

FeCl3

ppmp 0 0 0 280

Solid FeCl3 added

g 0.27 0.96 0 0

FeCl3 concentration in the reactor

ppmp 1,000 2,030 148 2,100

ppmp = Parts per million by weight

Example 1.

The distillation column of the distillation column was charged with a mixture of approximately 90 percent 1,1,1,2,3-pentachloropropane, with approximately 10 percent other miscellaneous chlorocarbons. Approximately 0.27 grams of solid anhydrous ferric chloride was added to the liquid, with stirring, giving a concentration of 1,000 ppm by weight in the distillation tails. The column pressure was adjusted to 37.2 kPa (280 torr), and sufficient heat was applied to the distillation flask to reflux the liquid in the column. A

Synthetic feed comprised of 45 percent of 1,1,1,2,3-pentachloropropane and 55 percent of various other chlorocarbons was continuously fed to the distillation flask to give a residence time of the liquid in the flask of distillation of approximately 4.5 hours. The synthetic feed did not contain ferric chloride. Liquid withdrawal from the reflux head was initiated simultaneously with the feed at a rate sufficient to maintain the level of liquid in the distillation flask. The speed of formation of

20 1,1,2,3-tetrachloropropene, measured by the composition of the distillation head liquid and the collection rate, was less than 0.02 mol / h, indicating that very little dehydrochlorination of the pentachloropropane. The temperature of the distillation tails during the test varied from 159 to 160 ° C.

Example 2

The distillation flask of a distillation column was charged with a mixture of about 96 percent of 1,1,1,2,3-pentachloropropane, with about four percent of other various chlorocarbons. Approximately 0.96 grams of solid anhydrous ferric chloride was added to the liquid, with stirring, to give a concentration of ferric chloride of 2,030 ppm by weight in the distillation tails. The column pressure was adjusted to 65.8 kPa (495 torr), and sufficient heat was applied to the distillation flask to reflux the liquid in the column. A synthetic feed composed of 90.8 percent of 1,1,1,2,3-pentachloropropane and 9.2 percent of various other chlorocarbons was fed continuously to the distillation flask in order to give a residence time of the liquid in the distillation flask for approximately 7 hours. The feed did not contain ferric chloride. Liquid withdrawal from the reflux head was initiated simultaneously with the feed at a rate sufficient to maintain the level of liquid in the distillation flask. The formation rate of 1,1,2,3-tetrachloropropene, measured by the composition of the distillation head liquid and the collection rate, reached a maximum of 0.49 mol / h, in 5.7 hours of the test time, as shown in Figure 5. The formation rate then began to steadily drop below 0.19 mol / h at 16 hours. The temperature of the distillation tails in the course of the test increased steadily from 173-177 �C.

Example 3

A feed mixture containing 1,1,1,2,3-pentachloropropane was prepared by the liquid phase chlorination of 1,1,1,3-tetrachloropropane in the presence of dissolved ferric chloride. The unpurified chlorination product, which contained approximately 80 percent of 1,1,1,2,3-pentachloropropane, 20 percent of other miscellaneous chlorocarbons, and 150 ppm by weight of ferric chloride, was charged to the distillation flask of the distillation column. No additional solid ferric chloride was added to the liquid. The column pressure was adjusted to 63.8 kPa (480 torr), and sufficient heat was applied to the distillation flask to reflux the liquid in the column. Then, a synthetic feed composed of 61 percent of 1,1,1,2,3-pentachloropropane and 39 percent other various chlorocarbons was fed continuously to the distillation flask to provide a residence time of the liquid in the flask distillation of approximately 8 hours. The feed did not contain ferric chloride. The extraction of the liquid from the reflux head was started simultaneously with the feeding at a speed sufficient to maintain the level of the liquid in the distillation flask. The formation rate of 1,1,2,3-tetrachloropropene, measured by the composition of the distillation head liquid and the liquid collection rate, reached a maximum of 0.24 mol / h at 8.2 hours of the runtime, as shown in Figure 5. The formation rate then fell rapidly to below 0.03 mol / h at 13 hours, indicating that the dehydrochlorination reaction had almost stopped. The temperature of the distillation tails in the course of the test increased steadily from 169-179 �C.

Example 4

A feed mixture containing mainly 1,1,1,2,3-pentachloropropane was prepared by the liquid phase chlorination of 1,1,1,3-tetrachloropropane in the presence of dissolved ferric chloride. The unrefined chlorination product, which contained approximately 80 percent of 1,1,1,2,3-pentachloropropane, 20 percent of other miscellaneous chlorocarbons, and 280 ppm by weight of ferric chloride, was charged to the distillation flask of the distillation column. No additional solid ferric chloride was added to the liquid. The column pressure was adjusted to 46.5 kPa (350 torr), and sufficient heat was applied to the distillation flask to reflux the liquid in the column. The chlorination product of unrefined trichloropropene containing 80 percent of 1,1,1,2,3-pentachloropropane, 20 percent of other miscellaneous chlorocarbons, and 280 ppm by weight of ferric chloride was fed from continuously to the distillation flask in order to provide a residence time of the liquid of approximately 8 hours. The extraction of the liquid from the reflux head was started simultaneously with the feeding at a speed sufficient to maintain the level of the liquid in the distillation flask. Liquid was removed from the distillation flask every 2-3 hours of operation. The volume of liquid removed was approximately seven percent of the volume of material fed in the same period of time. The formation rate of 1,1,2,3-tetrachloropropene, measured by the composition of the distillation head liquid and the collection rate, increased to more than 0.40 mol / h in five hours of test, as shown in Figure 5. The formation rate was maintained between 0.4 and 0.55 mol / h for more than 70 hours of operation, with no evidence of decrease. The temperature of the distillation tails during the test was maintained between 154-157 �C. The concentration of ferric chloride in the distillation tails rose to approximately 2,100 ppm by weight at 40 hours of operation and remained constant.

Examples 5-6 Semi-discontinuous reactions of 1,1,1,2,3-pentachloropropane

Example 5 - Without carbon tetrachloride.

A mixture of 655 ppm of ferric chloride in 99+% purity and 1,1,1,3-tetrachloropropane raw material was heated and stirred in a 1-liter flask at 54-60 ° C for 6.22 hours, while 0.68 to 0.82 moles of chlorine were fed per hour per kg of liquid feed. Hydrogen chloride left the reactor continuously, through a water-cooled condenser, and then through a pressure control valve. The reactor pressure was maintained at approximately 34.5-48.2 kPa (5-7 psig). Samples of the reactor liquid were taken periodically, with the following results:

Table 2: Results of Example 5

Weather

h 0.00 1.30 2.35 3.50 4.50 6.22

No. shows

53202501 53302701 53302703 53302801 53302803 53302805

Weight, total, postulated

g 817 820 835 815 845 909

Chlorine feed

mol / h / kg  0.68 0.75 0.82 0.79 0.74

Average temperature

�C 52.9 54.3 54.7 57.7 55.9

Concentrations

FeCl3

% in weigh 0.065 0.065 0.064 0.066 0.063 0.059

1,1,3-trichloro propene

% in weigh 0.00 0.14 2.57 22.14 14.80 1.09

1,1,1,3 tetrachloro propane

% in weigh 99.93 86.96 73.93 21.63 14.32 8.31

1,1,2,3 tetrachloro propene

% in weigh 0.00 0.05 0.21 0.46 0.62 0.93

1,1,1,2,3pentachloro propane

% in weigh 0.00 2.70 17.34 33.19 44.13 65.55

Total CG components

% in weigh 100.00 91.56 95.81 88.37 82.88 86.72

Useful product

Mol / kg 5.49 4.92 5.05 4.27 3.88 3.61

Performance over 1,1,1,3 tetrapropane

1,1,1,2,3pentachloro propane

% 2.3 14.9 27.9 38.4 61.4

Useful product

% 89.9 94.0 77.5 73.0 73.2

5 In this and in the following tables, "useful product" refers to the sum of 1,1,1,2,3-pentachloropropane, 1,1,2,3-tetrachloropropene, and 1,1,3-trichloropropene. The yields are calculated on the 1,1,1,3-tetrachloropropane fed. "GC" refers to the analysis by Gas Chromatography of the samples of the indicated liquid.

An important observation on this table is that the "useful product" then decreased in the sample at 2.35 hours from a yield of 94% over the 1,1,1,3-tetrachloropropane fed to 73%. Similarly, the 10 total GC components decreased from 96% to 2.35 hours to 87% at the end of 6.2 hours. The GC showed increasing amounts of components that, judging by retention times, boiled at temperatures considerably greater than 1,1,1,2,3-pentachloropropane. For example, the last sample, number 53302805, contained twenty-three components with longer retention times than 1,1,1,2,3-pentachloropropane, totaling 8.7% of the sample area. Therefore, products with high boiling points were produced at

15 undesirably high speeds.

Example 6- With carbon tetrachloride in the feed.

A mixture of 51.6% by weight of carbon tetrachloride and 48.3% by weight of 1,1,1,3-tetrachloropropane was stirred and heated with 608 ppm of ferric chloride. This experiment was operated for 4.75 hours, feeding 0.59 to 0.73 moles of chlorine per hour per kg of liquid feed, maintaining the temperature around 53-55 ° C.

Table 3: Results of Example 6

Weather

h 0.00 1.25 2.00 2.95 3.90 4.75

No. shows

53303101 53304401 53304403 53304405 53304501 53304504

Weight, total, postulated

g 893 903 914 938 965 965

Chlorine feed

mol / h / kg  0.62 0.73 0.71 0.69 0.59

Average temperature

�C 53.3 54.3 54.6 54.7 52.9

Pressure

kPa (psig) 39.3 (5.7) 37.9 (5.5) 34.4 (5.1) 34.4 (5.0) 39.3 (5.7)

Concentrations

FeCl3

% in weigh 0.061 0.060 0.059 0.058 0.056 0.056

Carbon tetrachloride

% in weigh 51.63 49.82 48.83 47.01 44.77 43.69

1,1,3-trichloro propene

% in weigh  0.09 5.38 4.93 0.04 0.03

1,1,1,3 tetrachloro propane

% in weigh 48.31 41.41 22.27 6.97 2.44 1.22

1,1,2,3 tetrachloro propene

% in weigh  0.10 0.35 0.66 0.65 0.07

1,1,1,2,3pentachloro propane

% in weigh  7.51 23.35 37.81 47.35 47.00

Total CG components

% in weigh 100.00 99.41 101.03 100.17 98.11 95.20

Useful product

Mol / kg 2.66 2.63 2.69 2.51 2.36 2.25

Performance over 1,1,1,3 tetrapropane

1,1,1,2,3pentachloro propane

% 13.2 41.6 69.1 89.1 88.4

Useful product

% 100.4 103.9 99.1 96.2 91.4

In this case, the total "useful product" decreased from 99% yield over 1,1,1,3-tetrachloropropane fed at 2.95 hours, to 91% yield at 4.75 hours. The last sample, 53304504, contained ten components that eluted after 1,1,1,2,3-pentachloropropane in the GC, totaling 2.7% of the area. The maximum yield of 1,1,1,2,3-pentachloropropane was 89% at 3.9 hours. The comparison of Example 6

with Example 5 it shows an improvement in the results caused by the presence of carbon tetrachloride in the feeds.

Examples 7-10 Continuous reactions of 1,1,1,2,3-pentachloropropane

Example 7

The equipment shown in Figure 6 was used.

For this experiment (test number 53315304) the feed mixture was produced in a pilot plant unit. The pilot plant unit reacted carbon and ethylene tetrachloride in a stirred 10 gallon vessel, in the presence of ferric chloride, iron metal, and tributyl phosphate. The reactor effluent was distilled to separate 1,1,1,3-tetrachloropropane and the lower boiling materials (the distillation head fraction) from the higher boiling materials, which included iron compounds and phosphorus The distillation head fraction (sample number 53313710) contained 13.6% by weight of carbon tetrachloride, 84.8% by weight of 1,1,1,3-tetrachloropropane, 0.23% by weight of chloroform, 0.08% by weight of 1-chlorobutane, 0.17% by weight of perchlorethylene, and 1.1% by weight of other volatile materials. It was a clear and colorless liquid.

Part of this fraction of the distillation head was placed in D1, shown in Figure 6. This material was fed into the reactor, through the P 1 pump, at 200 grams per hour. The solid ferric chloride was periodically weighed in D2, which was made of a system of polytetrafluoroethylene pipes with an outside diameter of 1/4 ". Approximately 0.3 grams of ferric chloride was added to the reactor each two hours of operation The average concentration of ferric chloride in the reactor liquid was 740 ppm by weight The chlorine was fed

through a system of polytetrafluoroethylene pipes with an outside diameter of 0.125 ”, which extended below

of the surface of the liquid. The ratio of the chlorine feed to 1,1,1,3-tetrachloropropane was 1.00 mol / mol. The reactor liquid was stirred at approximately 110 rpm. The temperature of the reactor liquid was maintained at approximately 77 ° C, and the pressure was maintained at 70 kPa (10 psig). The volume of the reactor liquid was approximately 1.05 liters, and the estimated liquid effluent flow rate was 0.155 liters per hour, so that the estimated rotation time was 6.8 hours. The chlorine and hydrogen chloride flows in the ventilation stream were measured through timed samples captured in potassium iodide solution. At the end of 15.0 hours of operation (approximately 2.0 liquid returns), a sample of the liquid effluent from the reactor was analyzed by gas chromatography.

The chlorine conversion was 99%; 1,1,1,3-tetrachloropropane conversion was 99%. The yields of 1,1,3-trichloropropene, 1,1,1,2,3-pentachloropropane, and 1,1,2,3-tetrachloropropene on the 1,1,1,3-tetrachloropropane fed were 2.0, 85, and 5.8 percent, respectively. The total yield of the four prominent high-boiling by-products was 3.3% by weight in the reactor effluent. It is believed that these by-products are hexachloropropane, two isomers of pentachlorohexene, and hexachlorohexadiene.

Example 8

The raw material (sample 53311408) for this example (test 53313101) was produced by the same pilot plant unit as the one mentioned above, and in the same way. It contained 15.69% by weight of carbon tetrachloride, 82.76% by weight of 1,1,1,3-tetrachloropropane, 0.18% by weight of chloroform, 0.03% by weight of 1-chlorobutane, 0.31 % by weight perchlorethylene, and 1.0% by weight of other volatile materials. The experiment was performed as Example 7, except for the following changes. The reactor temperature was maintained at 82 ° C; Liquid rotation time was 7.3 hours; the average concentration of ferric chloride was 550 ppm; The total test time was 2.1 rotations.

The chlorine conversion was 99%; 1,1,1,3-tetrachloropropane conversion was 99%. The yields of 1,1,3-trichloropropene, 1,1,1,2,3-pentachloropropane, and 1,1,2,3-tetrachloropropene on the 1,1,1,3-tetrachloropropane fed were 3,4, 82.9 and 8.1 percent, respectively. The yield of the same four prominent unwanted high boiling by-products was 4.2% by weight in the reactor effluent.

Example 9

The starting material for this example (test 53315701) was produced by the same pilot plant unit as the one mentioned above, and in the same way. However, carbon tetrachloride was then separated from 1,1,1,3-tetrachloropropane by distillation, yielding sample 53315501. The last material contained 0.06% by weight of carbon tetrachloride, 0.21% by weight. weight of 1,1,3-trichloropropene, 0.041% by weight perchlorethylene, 99.60% by weight of 1,1,1,3-tetrachloropropane, and 0.09% by weight of other volatile components. This material was placed in D1 and fed to the reactor. The experiment was performed as in Example 8, except for the difference in the raw material. The reactor temperature was maintained at 82 ° C; the rotation time of the liquid was 7.3 hours; the average concentration of ferric chloride was 510 ppm; The total test time was 2.1 rotations.

The chlorine conversion was 97%; 1,1,1,3-tetrachloropropane conversion was 99%. The yields of 1,1,3-trichloropropene, 1,1,1,2,3-pentachloropropane, and 1,1,2,3-tetrachloropropene on the 1,1,1,3-tetrachloropropane fed were 3,7, 76.7, and 7.6 percent, respectively. The yield of the usual four prominent unwanted high boiling by-products was 6.3% by weight in the reactor effluent. The comparison of this experiment with Example 8 shows a significant advantage for the raw material that

5 contained 15.7% by weight of carbon tetrachloride.

Example 10

The liquid raw material (sample 53315312) for this example (test 53317907) was produced by the same pilot plant unit of Example 7. It contained 22.46% by weight of carbon tetrachloride, 76.09% by weight of 1.1 , 1,3-tetrachloropropane, 0.23% by weight of chloroform, 0.09% by weight of 1-chlorobutane, 0.13% by weight perchlorethylene,

10 and 1.0% by weight of other volatile materials. The experiment was carried out at a higher temperature, with less ferric chloride catalyst, in relation to Example 7. The reactor temperature was maintained at 92 ° C; the rotation time of the liquid was 7.2 hours; the average concentration of ferric chloride was 180 ppm; The total test time was 2.0 rotations. The reactor pressure was 62-70 kPa (9-10 psig), as usual.

15 The chlorine conversion was 98%; 1,1,1,3-tetrachloropropane conversion was 97%. The yields of 1,1,3-trichloropropene, 1,1,1,2,3-pentachloropropane, and 1,1,2,3-tetrachloropropene on the 1,1,1,3-tetrachloropropane fed were 2,7, 85, and 5.7 percent, respectively. The yield of the four usual prominent unwanted high boiling by-products was 2.2% by weight in the reactor effluent.

Claims (20)

1. A process for the manufacture of 1,1,2,3-pentachloropropane, the process comprising: preparing 1,1,1,2,3-pentachloropropane by heating a reaction mixture comprising 1,1,1,3 tetrachloropropane, ferric chloride and chlorine to produce 1,1,1,2,3-pentachloropropane, in wherein the reaction mixture optionally further comprises carbon tetrachloride in an amount of up to 50% by weight of the reaction mixture; Y dehydrochlorinate 1,1,1,2,3-pentachloropropane in a dehydrochlorination reaction zone in the presence of ferric chloride to produce 1,1,2,3-tetachloropropene and hydrogen chloride, where 1, 1,2,3-tetrachloroprene and hydrogen chloride are removed from the hydrochlorination reaction zone through distillation during the course of the dehydrochlorination reaction.

2.

 The process of claim 1, wherein the ferric chloride is present in the reaction mixture in an amount in the range of from 10 to 1,000 ppm.

3.

 The process of claim 1, wherein at least a part of the process for the preparation of 1,1,1,2,3pentachloropropane occurs in equipment comprising a reaction zone, a separation zone that optionally comprises a distillation component , and a condensation zone.

Four.

 The process of claim 1, wherein the process for the preparation of 1,1,1,2,3-pentachloropropane further comprises substantially continuously feeding 1,1,1,3-tetrachloropropane and chlorine to a reaction zone that It contains ferric chloride.

5.

 The process of claim 4, wherein 1,1,1,3-tetrachloropropane and chlorine are introduced with a feed ratio of from 0.9 to 1.1 moles of chlorine per mole of tetrachloropropane.

6.

 The process of claim 1, wherein the hydrogen chloride is a co-product of the process and is removed from the reaction zone through a separation zone and a condensation zone, and wherein also the hydrogen chloride leaving of the reaction zone contains 1,1,3-trichloropropene or carbon tetrachloride or both 1,1,3-trichloropropene and carbon tetrachloride and 1,1,3-trichloropropene or carbon tetrachloride or both 1,1,3-trichloropropene and Carbon tetrachloride is recycled to the reaction zone through the condensation zone.

7.

The process of claim 1, further comprising subjecting at least a portion of the 1,1,2,3pentachloropropane formed to one or more purification steps.

8.

 The process of claim 1, wherein 10 to 20,000 parts per million by weight of ferric chloride are maintained in the dehydrochlorination reaction zone.

9.

 The process of claim 1, wherein the dehydrochlorination process is carried out using reactive distillation equipment, comprising a reaction zone, a separation zone, and a condensation zone, wherein 1,1, 2,3-tetrachloropropene and hydrogen chloride are removed from the dehydrochlorination reaction zone through the separation zone and the condensation zone.

10.

 The process of claim 9, wherein the temperature of the dehydrochlorination zone is 120 to 180 ° C, the pressure of the separation zone is in the range of 13 to 80 kPa (100 to 600 torr) and The temperature of the condensation zone is such that it causes the distilled 1,1,2,3-tetrachloropropene from the reaction zone to condense in a liquid.

eleven.

 The process of claim 1, wherein 1,1,1,2,3-pentachloropropane is contained within an unrefined 1,1,1,2,3pentachloropropane, wherein 1,1,1,2,3- Unrefined pentachloropropane comprises 1,1,1,2,3pentachloropropane, and at least one of ferric chloride, carbon tetrachloride, 1,1,3-trichloropropene, 1,1,1,3-tetrachloropropane, and 1,1,2 , 3-tetrachloropropene, where the process includes:

feed the unrefined 1,1,1,2,3-pentachloropropane to the dehydrochlorination reaction zone, to transform the unrefined 1,1,1,2,3-pentachloropropane into 1,1,2,3- tetrachloropropene and hydrogen chloride by dehydrochlorination, wherein 1,1,2,3-tetrachloropropene and hydrogen chloride are removed from the reaction zone during the course of the dehydrochlorination reaction; Y collect 1,1,2,3-tetrachloropropene.

12.

 The process of claim 11, wherein the unrefined 1,1,1,2,3-pentachloropropane is transformed into 1,1,2,3 tetrachloropropene by reactive distillation, wherein the reactive distillation occurs in the equipment comprising an area reaction zone, a separation zone, and a condensation zone, wherein 1,1,2,3-tetrachloropropene and hydrogen chloride are removed from the reaction zone through the separation zone and the zone of

condensation, whereby at least some of the 1,1,2,3-tetrachloropropene separates as a liquid condensate from hydrogen chloride vapor, producing purified hydrogen chloride vapor and 1,1,2,3-tetrachloropropene without refine.

13.

 The process of claim 11, wherein the at least a portion of the unrefined 1,1,2,3-tetrachloropropene is subjected to one or more purification steps.

14.

 The process of claim 11, wherein 10 to 20,000 ppm by weight of ferric chloride are maintained in the reaction zone.

fifteen.

 The process of claim 11, wherein a liquid reaction mixture, comprising unreacted 1,1,1,2,3 pentachloropropane, ferric chloride, nonvolatile material, and high boiling by-products, is removed. periodically or continuously from the reaction zone and at least a part of the 1,1,1,2,3pentachloropropane that has not reacted contained in the removed reaction mixture is separated from at least some of the other components of the mixture of reaction, and then recycled to the reaction zone.

16.

 The process of claim 1, comprising:

(i)

 reacting carbon tetrachloride with ethylene in the presence of iron chlorides, iron metal, and a trialkyl phosphate to produce an unrefined product containing 1,1,1,3-tetrachloropropane;

(ii)

 distilling said unrefined product to produce a distillation head stream and a distillation tail stream, the distillation head stream 1,1,1,3-tetrachloropropane and unreacted carbon tetrachloride comprising, and comprising the stream of 1,1,1,3-tetrachloropropane distillation tails;

(iii) reacting the stream of the distillation head with chlorine in the presence of ferric chloride to produce unrefined 1,1,1,2,3-pentachloropropane;

(iv)

adding 1,1,1,2,3-unrefined pentachloropropane from step (iii) to a reaction zone, which is part of a reactive distillation process equipment comprising a reaction zone, a zone of separation, and a condensation zone, and dehydrochlorinate the unrefined 1,1,1,2,3-pentachloropropane to form hydrogen chloride and 1,1,2,3-tetrachloropropene, and remove hydrogen chloride and 1,1, 2,3-tetrachloropropene from the reaction zone during the course of dehydrochlorination by distillation, and

(v)

 collect the 1,1,2,3-tetrachloropropene product.

17.

 The process of claim 16, wherein the unrefined 1,1,1,2,3-pentachloropropane liquid product of step (iii) is fed directly without purification to the reaction zone of step (iv).

18.

 The process of claim 16, wherein at least a portion of the unrefined liquid 1,1,2,3-tetrachloropropene is subjected to one or more purification steps.

19.

 The process of claim 16, wherein 10 to 1,000 ppm by weight of ferric chloride are maintained in the reaction zone of step (iii) or 10 to 20,000 ppm by weight of ferric chloride are maintained in the reaction zone of step (iv).

twenty.

 The process of claim 16, wherein the liquid reaction mixture in the reaction zone of step (iv) contains unreacted 1,1,1,2,3-pentachloropropane and ferric chloride, and at least Some of this liquid mixture is removed periodically or continuously from the reaction zone, and at least a portion of the 1,1,1,2,3pentachloropropane that has not reacted contained in the removed reaction mixture is separated from at least some of the other components of the reaction mixture, and then recycled to the reaction zone.

Figure 1. A process of the invention for making 1,1,1,2,3-pentachloropropane Figure 2. A process of the invention for making 1,1,2,3-tetrachloropropene Figure 3. A process of the invention for making 1,1,2,3-tetrachloropropene Figure 4. A process of the invention for making 1,1,2,3-tetrachloropropene Figure 5. Results of Examples 2-4 Figure 6. Laboratory equipment for the continuous reaction of HCC240db